EP0622410B1 - Medical articles and process therefor - Google Patents
Medical articles and process therefor Download PDFInfo
- Publication number
- EP0622410B1 EP0622410B1 EP94302488A EP94302488A EP0622410B1 EP 0622410 B1 EP0622410 B1 EP 0622410B1 EP 94302488 A EP94302488 A EP 94302488A EP 94302488 A EP94302488 A EP 94302488A EP 0622410 B1 EP0622410 B1 EP 0622410B1
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- European Patent Office
- Prior art keywords
- mold
- blend
- cycle time
- article
- syndiotactic
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/12—Syndiotactic polypropylene
Definitions
- This invention relates to plastic articles, and more particularly relates to medical articles of syndiotactic polypropylene compositions and a process for their manufacture.
- Molding is a process in which melted or plasticized polymeric material is forced into a mold where it is held until removed in a solid state having a shape which duplicates the cavity of the mold.
- the process consists of three basic operations: 1) raising the temperature of the plastic to a point where it will flow under pressure into the mold cavity, (2) allowing the plastic to solidify in the mold (conventionally referred to as hold time) while maintaining pressure during removal of heat, and (3) opening the mold to eject the plastic permanently frozen in the shape of the mold.
- the productivity of the molding operation depends on the speed of melting the plastic, the speed of injection and ejection, and the hold time required to cool and solidify the product in the mold.
- cycle time is defined as the time required for one complete operation of a molding press from closing time to closing time.
- the largest part of the cycle time is the hold time, which generally accounts for up to 80% of the cycle time, and may be as high as 95%.
- Prolypropylene has long been used in molding and extruding operations for articles such as containers and films for the food packaging industry, and is known to exist in three forms.
- IPP isotactic polypropylene
- SPP syndiotactic polypropylene
- APP Atactic polypropylene
- APP is essentially a waxy product of low melting point whereas SPP and IPP are crystalline and of higher melting point.
- European Patent Application 428,972 discloses a method to improve the transparency of a sheet prepared with the Ewen et al. SPP.
- a polypropylene composition includes a blend of at least 85% SPP and up to 15% IPP. (In this disclosure, all percentages are by weight unless otherwise indicated).
- the composition may be molded into a medical article by a molding process of exceptionally high productivity resulting from an unexpected acceleration of the rate of crystallisation of pure SPP achieved by blending the SPP with the IPP.
- the process includes the steps of blending the SPP and IPP, melting the blend, injecting the melted blend into a mold, holding the blend in the mold until the blend crystallises and removing the solidified article from the mold. More, particularly, the present invention provides a method to prepare a medical article comprising;
- a preferred method comprises;
- the molded article of the invention has excellent tensile strength, modulus and impact resistance, is of exceptional clarity, and may be clear enough to use without adding a separate clarifying agent to the composition or including a post-molding processing operation.
- the molding operation itself is of high productivity due to the rapid crystallization of the blend which greatly reduces the hold time in the mold.
- the figure is a plot illustrating the relationship of the ratio of the components of the composition to the molding cycle time.
- the present invention contemplates any medical article which can be molded from a polymeric material.
- Preferred articles are those requiring a see-through capacity.
- the most preferred articles have a wall thickness of about 2 mm or less, such as blood collection tubes, centrifuge tubes, culture bottles, syringe stoppers and barrels and the like.
- the composition of the invention may be prepared by blending the SPP of U.S. Patent No. 4,892,851 with a suitable commercial IPP.
- the SPP may have a syndiotactic index of 80% or higher.
- a preferred SPP may have an index of 85%, most preferably 90% or higher.
- a convenient indicator of a suitable IPP is the peak melting point of the IPP wherein a higher melting point indicates higher isotactic purity.
- an IPP having a peak melting point of 166°C or higher, as determined by conventional differential scanning colorimity (DSC) may be blended with the SPP in the molding composition.
- a preferred IPP has a melting point of 168°C or higher.
- the most preferred IPP is a material known in the art as a super high IPP, and has a DSC peak melting point in the range of 168-70°C.
- the IPP may be present in the blend at a concentration of 0.1 to 15%, preferably 2 to 8%.
- composition may additionally include effective quantities of any conventional additive as known in the polyolefin art such as, for example radiation stabilizers, fillers, coloring agents, antistatic materials, wetting agents, nucleators and the like, providing the desired physical properties, clarity, and moldability, are not adversely affected. Determination of suitable quantities of these additives is well within the purview of one of ordinary skill in the polymer and molding arts.
- the SPP and IPP may be blended by any conventional melt compounding technique, preferably by twin screw extruding, prior to molding. Addition of the IPP greatly improves the moldability and reduces the high molding cycle time of the SPP by up to 12 fold. This improvement alone is sufficient to convert an inefficient and unprofitable molding operation to one of high productivity and competitiveness.
- Blending of the IPP into the SPP was found to have no deleterious effect on the physical properties of the SPP and in fact was found to result in about 10-20% improvement in strength.
- Table I sets forth the physical data obtained using ASTM procedure D638. SPP 5% blend tensile (kg/cm 2 ) 261 311 modulus (kg/cm 2 ) 1346 1787 impact resistance (kg/cm 2 ) 48 77
- Clarity for the plastic articles of the invention may be given as the conventional percent haze value and may be determined by ASTM procedure D-1003 on 1 and 2 mm step plaques.
- Cycle time may be determined on 2 mm step plaques as described in Example 5.
- melts were at 392° F (200°C) when injected into the mold, and the mold was at 70°F (21°C). All melts contained 0.25% of bis(p-methylbenzylidene) sorbitol nucleator, (MILLAD, 3940, Millikin Research Corp., Spartanburg, N.C.)
- a sample of SPP of 90% syndiotactic index was obtained from Exxon, Houston, TX, melted and injected into the Arburg ALLROUNDERTM injection molding unit to prepare a 1 and 2 mm step plaque. Because of slow crystallization, a cycle time of 320 sec. was required for molding (since a step plaque was molded, the cycle time is given for the 2 mm thick section). The plaque was ejected with difficulty due to sticking and had a wavy surface. Haze values of 2.5 and 11.8 were determined be ASTM D 1003 using a Hunterlab Colorimeter Model D25P-2.
- Blends containing 95% of SPP of 90% syndiotactic index and 5% of the commercial IPP samples of Example II were prepared by melt compounding in a twin screw extruder (Haake Buchler Instruments, Inc.). The blended melts were molded into 1 and 2 mm step plaques and the cycle time and haze values determined. The data are set forth in Table III.
- Blends of SPP of 90% syndiotactic index and the Chisso IPP were prepared by melt compounding into compositions of various weight percent as described in Example III. The melts were molded into 1 and 2 mm step plaques. Cycle times and haze values are given below in Table IV and a plot of cycle time against composition is given in the Figure.
- cycle time reaches a minimum at about 7.5 weight percent of IPP and then, surprisingly, increases with increasing IPP.
- cycle times are reduced about 12 fold at the 2.5 to 7.5 weight percent level.
- the most preferred composition of the invention when both haze and cycle time are considered is about 5.0 percent IPP.
- Cycle times were determined by injection molding 2"x3" step-plaques using a single-screw Arburg 20 ton machine.
- the thin side of the plaque was 1 mm and the thick side was 2mm.
- the melt temperature was adjusted to an average of 392°F and the mold was cooled to 60°F.
- Conditions and cycle time were adjusted to obtain a uniform plaque that did not stick to the mold cavity when ejected. The time corresponding to this condition was recorded as cycle time.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Materials For Medical Uses (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
- Infusion, Injection, And Reservoir Apparatuses (AREA)
- Media Introduction/Drainage Providing Device (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Description
1. Field of the Invention. This invention relates
to plastic articles, and more particularly relates to
medical articles of syndiotactic polypropylene
compositions and a process for their manufacture.
2. Background of the Invention. Molding is a
process in which melted or plasticized polymeric material
is forced into a mold where it is held until removed in a
solid state having a shape which duplicates the cavity of
the mold. The process consists of three basic operations:
1) raising the temperature of the plastic to a point where
it will flow under pressure into the mold cavity,
(2) allowing the plastic to solidify in the mold
(conventionally referred to as hold time) while
maintaining pressure during removal of heat, and
(3) opening the mold to eject the plastic permanently
frozen in the shape of the mold. The productivity of the
molding operation depends on the speed of melting the
plastic, the speed of injection and ejection, and the hold
time required to cool and solidify the product in the
mold. Thus, in the molding art, cycle time is defined as
the time required for one complete operation of a molding
press from closing time to closing time. In most molding
operations, the largest part of the cycle time is the hold
time, which generally accounts for up to 80% of the cycle
time, and may be as high as 95%.
Prolypropylene has long been used in molding and
extruding operations for articles such as containers and
films for the food packaging industry, and is known to
exist in three forms. In isotactic polypropylene (IPP),
the methyl groups are attached to the tertiary carbon
atoms of successive monomeric units on the same side of a
hypothetical plane through the polymer chain.
Syndiotactic polypropylene (SPP) has the methyl groups
attached on alternating sides of the polymer chain.
Atactic polypropylene (APP) has the methyl groups attached
randomly with respect to the polymer chain. APP is
essentially a waxy product of low melting point whereas
SPP and IPP are crystalline and of higher melting point.
Conventional molding and extruding grades of
polypropylene are substantially isotactic, and, depending
on the polymerization catalyst and conditions, contain
various amounts of monomeric units having other
configurations.
SPP, although known for many years in various degrees
of syndiotactic purity, has been only a laboratory
curiosity until recently. A new crystalline SPP of
exceptionally high syndiotacticity purity prepared by a
process using syndiospecific metallocene catalysts is
disclosed by Ewen et al. in US Patent No. 4,892,851,
incorporated herein by reference. The product is stated
to have a higher melting point and lower heat of
crystallization than IPP.
European Patent Application 428,972 discloses a
method to improve the transparency of a sheet prepared
with the Ewen et al. SPP.
A polypropylene composition includes a blend of at
least 85% SPP and up to 15% IPP. (In this disclosure, all
percentages are by weight unless otherwise indicated).
The composition may be molded into a medical article by a
molding process of exceptionally high productivity resulting from an unexpected
acceleration of the rate of crystallisation of pure SPP achieved by blending the SPP
with the IPP. The process includes the steps of blending the SPP and IPP, melting the
blend, injecting the melted blend into a mold, holding the blend in the mold until the
blend crystallises and removing the solidified article from the mold. More, particularly,
the present invention provides a method to prepare a medical article comprising;
A preferred method comprises;
The molded article of the invention has excellent
tensile strength, modulus and impact resistance, is of
exceptional clarity, and may be clear enough to use
without adding a separate clarifying agent to the
composition or including a post-molding processing
operation. The molding operation itself is of high
productivity due to the rapid crystallization of the blend
which greatly reduces the hold time in the mold.
The figure is a plot illustrating the relationship of
the ratio of the components of the composition to the
molding cycle time.
While this invention is satisfied by embodiments in
many different forms, there will herein be described in
detail preferred embodiments of the invention, with the
understanding that the present disclosure is to be
considered as exemplary of the principles of the invention
and is not intended to limit the invention to the
embodiments illustrated and described.
The present invention contemplates any medical
article which can be molded from a polymeric material.
Preferred articles are those requiring a see-through
capacity. The most preferred articles have a wall
thickness of about 2 mm or less, such as blood collection
tubes, centrifuge tubes, culture bottles, syringe stoppers
and barrels and the like.
It has been found that melted SPP having a
syndiotactic index of 80 percent or higher crystallizes
very slowly, requiring a long hold time in the mold before
ejection. Conventional nucleators, such as sorbitos, do
not shorten the mold cycle time. Thus, in order to mold
a plaque about 2 mm thick from the SPP of the aforementioned
U.S. Patent No. 4,892,851, a cycle time of about
320 sec. is required. Further, molding of the SPP is
difficult and molded plaques, while of satisfactory
clarity, are non-uniform and have wavy surfaces. After
cooling and crystallization, the plaques stick to the mold
making ejection difficult.
Conventional commercially available IPP, in contrast,
has been found to mold easily with a short cycle time of
about 15 sec. for 2 mm molded plaques. These plaques have
poor clarity, as shown by an average haze of 24.7 and 50.6
for 1 and 2 mm thick plaques respectively when tested by
ASTM D1003.
The composition of the invention may be prepared by
blending the SPP of U.S. Patent No. 4,892,851 with a
suitable commercial IPP. The SPP may have a syndiotactic
index of 80% or higher. A preferred SPP may have an index
of 85%, most preferably 90% or higher. A convenient
indicator of a suitable IPP is the peak melting point of
the IPP wherein a higher melting point indicates higher
isotactic purity. In accordance with the present
invention, an IPP having a peak melting point of 166°C or
higher, as determined by conventional differential
scanning colorimity (DSC), may be blended with the SPP in
the molding composition. A preferred IPP has a melting
point of 168°C or higher. The most preferred IPP is a
material known in the art as a super high IPP, and has a
DSC peak melting point in the range of 168-70°C. The IPP
may be present in the blend at a concentration of 0.1 to
15%, preferably 2 to 8%.
The composition may additionally include effective
quantities of any conventional additive as known in the
polyolefin art such as, for example radiation stabilizers,
fillers, coloring agents, antistatic materials, wetting
agents, nucleators and the like, providing the desired
physical properties, clarity, and moldability, are not
adversely affected. Determination of suitable quantities
of these additives is well within the purview of one of
ordinary skill in the polymer and molding arts.
The SPP and IPP may be blended by any conventional
melt compounding technique, preferably by twin screw
extruding, prior to molding. Addition of the IPP greatly
improves the moldability and reduces the high molding
cycle time of the SPP by up to 12 fold. This improvement
alone is sufficient to convert an inefficient and
unprofitable molding operation to one of high productivity
and competitiveness.
Testing of the blends of the invention for physical
properties, clarity and mold cycle times was performed on
molded 1 and 2 mm step plaques. Blending of the IPP into
the SPP was found to have no deleterious effect on the
physical properties of the SPP and in fact was found to
result in about 10-20% improvement in strength. Table I
sets forth the physical data obtained using ASTM procedure
D638.
| SPP | 5% blend | |
| tensile (kg/cm2) | 261 | 311 |
| modulus (kg/cm2) | 1346 | 1787 |
| impact resistance (kg/cm2) | 48 | 77 |
Clarity for the plastic articles of the invention may
be given as the conventional percent haze value and may be
determined by ASTM procedure D-1003 on 1 and 2 mm step
plaques.
Cycle time may be determined on 2 mm step plaques as
described in Example 5.
The following examples are given to further describe
the invention but are not to be considered as limitative
of the invention. In the examples, all melts were at 392°
F (200°C) when injected into the mold, and the mold was at
70°F (21°C). All melts contained 0.25% of bis(p-methylbenzylidene)
sorbitol nucleator, (MILLAD, 3940, Millikin
Research Corp., Spartanburg, N.C.)
A sample of SPP of 90% syndiotactic index was
obtained from Exxon, Houston, TX, melted and injected into
the Arburg ALLROUNDER™ injection molding unit to prepare a
1 and 2 mm step plaque. Because of slow crystallization,
a cycle time of 320 sec. was required for molding (since a
step plaque was molded, the cycle time is given for the 2
mm thick section). The plaque was ejected with difficulty
due to sticking and had a wavy surface. Haze values of
2.5 and 11.8 were determined be ASTM D 1003 using a
Hunterlab Colorimeter Model D25P-2.
Various commercial or experimental IPPs were obtained
and peak melting points were determined by DSC. The
samples were molded into 1 and 2 mm thick step plaques
using the ALLROUNDER™ injection molding unit. Molding and
ejection were easy, and cycle times of between 13 and 18
sec. were obtained. The haze values of these products is
given below in Table II.
| IPP SAMPLE | mp | HAZE (%) | ||
| 1 mm | 2 mm | |||
| (1) | Sumitono WF605MB | 167.33 | 16.5 | 51.8 |
| (2) | Amoco 9439 | 166.33 | 12.0 | 46.6 |
| (3) | Exxon (high isotactic) | 167.67 | 14.9 | 46.9 |
| (4) | Chisso IPP (K-5028) | 168.0 | 10.3 | 34.0 |
| (5) | Himont PF-091 | 163.0 | 69.8 | 74.0 |
Blends containing 95% of SPP of 90% syndiotactic
index and 5% of the commercial IPP samples of Example II
were prepared by melt compounding in a twin screw extruder
(Haake Buchler Instruments, Inc.). The blended melts
were molded into 1 and 2 mm step plaques and the cycle
time and haze values determined. The data are set forth in
Table III.
| BLEND | CYCLE TIME (sec) | HAZE (%) | ||
| 1 mm | 2 mm | |||
| 1) | SPP-Chisso | 28 | 4.0 | 11.7 |
| 2) | SPP-Amoco | 50 | 8.5 | 14.7 |
| 3) | SPP-Sumitomo | 46 | 7.0 | 13.2 |
| 4) | SPP-Exxon | 79 | 6.7 | 13.8 |
| 5) | SPP-Himont | 145 | 5.8 | 12.6 |
It is seen from the table that by blending only 5%
IPP into the SPP, the cycle time is reduced from 320 sec
for pure SPP (Example I) by factors ranging from 2 to 12
fold. Haze values were somewhat higher than SPP for the 1
mm plaques, but virtually unchanged for the 2 mm plaques.
Molding was generally very satisfactory with only slight
sticking during ejection in blends 2 and 5. Thus, By
blending small percentages of IPP into the SPP, the
molding problems encountered in Example I with pure SPP
were overcome, cycle times were reduced five fold, and
haze was only marginally increased.
Blends of SPP of 90% syndiotactic index and the
Chisso IPP were prepared by melt compounding into
compositions of various weight percent as described in
Example III. The melts were molded into 1 and 2 mm step
plaques. Cycle times and haze values are given below in
Table IV and a plot of cycle time against composition is
given in the Figure.
| SAMPLE | HAZE | CYCLE TIME (sec) | ||
| SPP (%) | IPP (%) | 1mm | 2mm | 2mm |
| 100 | 0 | 2.5 | 11.8 | 320 |
| 99 | 1 | 39.4 | ||
| 97.5 | 2.5 | 7.6 | 15.2 | 29 |
| 95 | 5 | 4.0 | 11.7 | 28 |
| 92.5 | 7.5 | 7.4 | 15.0 | 23 |
| 90 | 10 | 32.1 | ||
| 85 | 15 | 6.5 | 21.1 | 43 |
| 60 | 40 | 24.4 | ||
| 40 | 60 | 19.9 | ||
| 0 | 100 | 10.3 | 34 | 13 |
From the data in Table IV, it is seen that cycle time
reaches a minimum at about 7.5 weight percent of IPP and
then, surprisingly, increases with increasing IPP. Using
this preferred IPP of melting point 168°C, cycle times are
reduced about 12 fold at the 2.5 to 7.5 weight percent
level. The most preferred composition of the invention
when both haze and cycle time are considered is about 5.0
percent IPP.
Cycle times were determined by injection molding
2"x3" step-plaques using a single-screw Arburg 20 ton
machine. The thin side of the plaque was 1 mm and the
thick side was 2mm. The melt temperature was adjusted to
an average of 392°F and the mold was cooled to 60°F.
Conditions and cycle time were adjusted to obtain a
uniform plaque that did not stick to the mold cavity when
ejected. The time corresponding to this condition was
recorded as cycle time.
Claims (8)
- A medical article comprising a molded blend of syndiotactic polypropylene having a syndiotactic index of at least 85 percent and about 0. 1 to 15% by weight of an isotactic polypropylene having a peak melting point of 166°C or higher, said blend having a molding cycle time which is at least four fold lower than the molding cycle time of the syndiotactic polypropylene component of the blend.
- The article of claim 1 which is a tube.
- The article of claim 1 which is a syringe barrel.
- A medical article according to claim 1 and comprising a molded blend of syndiotactic polypropylene having a syndiotactic index of at least 90 percent and about 2.5 to 7.5% by weight of an isotactic polypropylene having a peak melting point of about 168°C or higher, said blend having a molding cycle time which is at least ten fold lower than the molding cycle time of the syndiotactic polypropylene component of the blend.
- A method to prepare a medical article comprising;a) injecting a melted blend of syndiotactic polypropylene having a syndiotactic index of at least 85 percent and about 1 to 10 percent by weight of an isotactic polypropylene having a peak melting of at least 166°C into a mold;b) holding said blend in said mold until said blend crystallises in said mold to give an article having the shape of said mold; andc) ejecting said article from said mold, wherein method steps (a) to (c) are complete in a cycle time at least four fold less than the cycle time required to complete steps (a) to (c) with the pure syndiotactic polypropylene used in a step (a).
- The method of claim 6 wherein said article is a tube.
- The method of claim 6 wherein said article is a syringe barrel.
- A method according to claim 5 and comprising;a) injecting a melted blend of syndiotactic polypropylene having a syndiotactic index of at least 90 percent and about 2.5 to 7.5% by weight of an isotactic polypropylene having a peak melting point of at least 168°C or higher into a mold;b) holding said blend in said mold until said blend crystallises in said mold to give an article having the shape of said mold; andc) ejecting said article from said mold, wherein method steps (a) to (c) are complete in a cycle time at least ten fold less than the cycle time required to complete steps (a) to (c) with the pure syndiotactic polypropylene used in step (a).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US5447693A | 1993-04-30 | 1993-04-30 | |
| US54476 | 2002-01-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0622410A1 EP0622410A1 (en) | 1994-11-02 |
| EP0622410B1 true EP0622410B1 (en) | 1998-06-17 |
Family
ID=21991351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94302488A Expired - Lifetime EP0622410B1 (en) | 1993-04-30 | 1994-04-08 | Medical articles and process therefor |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US5603696A (en) |
| EP (1) | EP0622410B1 (en) |
| JP (1) | JP2608681B2 (en) |
| CA (1) | CA2120315C (en) |
| DE (1) | DE69411075T2 (en) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2120315C (en) * | 1993-04-30 | 2001-05-15 | Joel L. Williams | Medical articles and process therefor |
| EP0650816A1 (en) * | 1993-10-28 | 1995-05-03 | Mitsui Toatsu Chemicals, Incorporated | Method for injection molding blends of syndiotactic polypropylene and isotactic polypropylene and molded products obtained thereby |
| US5510075A (en) * | 1993-11-04 | 1996-04-23 | Becton, Dickinson And Company | Mold process for syndiotactic polypropylene |
| JP2594231B2 (en) * | 1994-05-09 | 1997-03-26 | 日本ピラー工業株式会社 | Gland packing |
| US6407177B1 (en) * | 1995-06-07 | 2002-06-18 | Fina Technology, Inc. | Polypropylene blend |
| DE69701819T2 (en) * | 1996-02-12 | 2000-10-12 | Fina Research S.A., Seneffe | Polypropylene fibers |
| US6680091B2 (en) * | 1996-12-23 | 2004-01-20 | Novo Nordisk A/S | Medicament container of polymer of cyclic hydrocarbon for storing a liquid medicament |
| US6143683A (en) * | 1997-04-09 | 2000-11-07 | Fina Technology, Inc. | Metallocene catalyst and catalyst system for polymerizing an olefin having at least 3 carbon atoms |
| US6074590A (en) * | 1997-07-28 | 2000-06-13 | Fina Technology, Inc. | Process of making a bicomponent fiber |
| DE19738051A1 (en) * | 1997-09-01 | 1999-03-04 | Targor Gmbh | Injection molded article made of metallocene polypropylene |
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| US7358505B2 (en) | 1998-09-15 | 2008-04-15 | Baxter International Inc. | Apparatus for fabricating a reconstitution assembly |
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-
1994
- 1994-03-30 CA CA002120315A patent/CA2120315C/en not_active Expired - Fee Related
- 1994-04-08 DE DE69411075T patent/DE69411075T2/en not_active Expired - Fee Related
- 1994-04-08 EP EP94302488A patent/EP0622410B1/en not_active Expired - Lifetime
- 1994-05-02 JP JP6093395A patent/JP2608681B2/en not_active Expired - Fee Related
-
1995
- 1995-01-05 US US08/369,971 patent/US5603696A/en not_active Expired - Fee Related
-
1996
- 1996-07-19 US US08/683,936 patent/US5720916A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH073088A (en) | 1995-01-06 |
| EP0622410A1 (en) | 1994-11-02 |
| CA2120315A1 (en) | 1994-10-31 |
| DE69411075D1 (en) | 1998-07-23 |
| CA2120315C (en) | 2001-05-15 |
| US5720916A (en) | 1998-02-24 |
| DE69411075T2 (en) | 1998-12-10 |
| JP2608681B2 (en) | 1997-05-07 |
| US5603696A (en) | 1997-02-18 |
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